HANDBOOK OF HYDROTHERMAL TECHNOLOGY A Technology for Crystal Growth and Materials Processing by K Byrappa University of Mysore Manasagangotri Mysore, India and Masahiro Yoshimura Tokyo Institute of Technology Yokohama, Japan NOYES PUBLICATIONS Park Ridge, New Jersey, U.S.A WILLIAM ANDREW PUBLISHING, LLC Norwich, New York, U.S.A JMR 10-Nov-00 Copyright © 2001 by Noyes Publications No part of this book may be reproduced or utilized in any form or by any means, electronic or mechanical, including photocopying, recording or by any information storage and retrieval system, without permission in writing from the Publisher Library of Congress Catalog Card Number: 00-021998 ISBN: 0-8155-1445-X Printed in the United States Published in the United States of America by Noyes Publications / William Andrew Publishing, LLC 13 Eaton Avenue Norwich, NY 13815 1-800-932-7045 www.knovel.com 10 Library of Congress Cataloging-in-Publication Data Byrappa, K Handbook of Hydrothermal Technology / by K Byrappa and Masahiro Yoshimura p cm Includes bibliographical references and index ISBN 0-8155-1445-X Crystallization Crystal growth I Title QD921.B97 2001 548'.5 dc21 00-021998 CIP To Sunitha and Akiko NOTICE To the best of our knowledge the information in this publication is accurate; however the Publisher does not assume any responsibility or liability for the accuracy or completeness of, or consequences arising from, such information This book is intended for informational purposes only Mention of trade names or commercial products does not constitute endorsement or recommendation for use by the Publisher Final determination of the suitability of any information or product for use contemplated by any user, and the manner of that use, is the sole responsibility of the user We recommend that anyone intending to rely on any recommendation of materials or procedures mentioned in this publication should satisfy himself as to such suitability, and that he can meet all applicable safety and health standards vi MATERIALS SCIENCE AND PROCESS TECHNOLOGY SERIES Series Editors Gary E McGuire, Microelectronics Center of North Carolina Stephen M Rossnagel, IBM Thomas J Watson Research Center Rointan F Bunshah, University of California, Los Angeles (1927–1999), founding editor Electronic Materials and Process Technology CHARACTERIZATION OF SEMICONDUCTOR MATERIALS, Volume 1: edited by Gary E McGuire CHEMICAL VAPOR DEPOSITION FOR MICROELECTRONICS: by Arthur Sherman CHEMICAL VAPOR DEPOSITION OF TUNGSTEN AND TUNGSTEN SILICIDES: by John E J Schmitz CHEMISTRY OF SUPERCONDUCTOR MATERIALS: edited by Terrell A Vanderah CONTACTS TO SEMICONDUCTORS: edited by Leonard J Brillson DIAMOND CHEMICAL VAPOR DEPOSITION: by Huimin Liu and David S Dandy DIAMOND FILMS AND COATINGS: edited by Robert F Davis DIFFUSION PHENOMENA IN THIN FILMS AND MICROELECTRONIC MATERIALS: edited by Devendra Gupta and Paul S Ho ELECTROCHEMISTRY OF SEMICONDUCTORS AND ELECTRONICS: edited by John McHardy and Frank Ludwig ELECTRODEPOSITION: by Jack W Dini HANDBOOK OF CARBON, GRAPHITE, DIAMONDS AND FULLERENES: by Hugh O Pierson HANDBOOK OF CHEMICAL VAPOR DEPOSITION, Second Edition: by Hugh O Pierson HANDBOOK OF COMPOUND SEMICONDUCTORS: edited by Paul H Holloway and Gary E McGuire HANDBOOK OF CONTAMINATION CONTROL IN MICROELECTRONICS: edited by Donald L Tolliver HANDBOOK OF DEPOSITION TECHNOLOGIES FOR FILMS AND COATINGS, Second Edition: edited by Rointan F Bunshah HANDBOOK OF HARD COATINGS: edited by Rointan F Bunshah HANDBOOK OF ION BEAM PROCESSING TECHNOLOGY: edited by Jerome J Cuomo, Stephen M Rossnagel, and Harold R Kaufman HANDBOOK OF MAGNETO-OPTICAL DATA RECORDING: edited by Terry McDaniel and Randall H Victora HANDBOOK OF MULTILEVEL METALLIZATION FOR INTEGRATED CIRCUITS: edited by Syd R Wilson, Clarence J Tracy, and John L Freeman, Jr HANDBOOK OF PLASMA PROCESSING TECHNOLOGY: edited by Stephen M Rossnagel, Jerome J Cuomo, and William D Westwood HANDBOOK OF POLYMER COATINGS FOR ELECTRONICS, Second Edition: by James Licari and Laura A Hughes HANDBOOK OF REFRACTORY CARBIDES AND NITRIDES: by Hugh O Pierson HANDBOOK OF SEMICONDUCTOR SILICON TECHNOLOGY: edited by William C O’Mara, Robert B Herring, and Lee P Hunt vii viii Series HANDBOOK OF SEMICONDUCTOR WAFER CLEANING TECHNOLOGY: edited by Werner Kern HANDBOOK OF SPUTTER DEPOSITION TECHNOLOGY: by Kiyotaka Wasa and Shigeru Hayakawa HANDBOOK OF THIN FILM DEPOSITION PROCESSES AND TECHNIQUES: edited by Klaus K Schuegraf HANDBOOK OF VACUUM ARC SCIENCE AND TECHNOLOGY: edited by Raymond L Boxman, Philip J Martin, and David M Sanders HANDBOOK OF VLSI MICROLITHOGRAPHY: edited by William B Glendinning and John N Helbert HIGH DENSITY PLASMA SOURCES: edited by Oleg A Popov HYBRID MICROCIRCUIT TECHNOLOGY HANDBOOK, Second Edition: by James J Licari and Leonard R Enlow IONIZED-CLUSTER BEAM DEPOSITION AND EPITAXY: by Toshinori Takagi MOLECULAR BEAM EPITAXY: edited by Robin F C Farrow SEMICONDUCTOR MATERIALS AND PROCESS TECHNOLOGY HANDBOOK: edited by Gary E McGuire ULTRA-FINE PARTICLES: edited by Chikara Hayashi, R Ueda and A Tasaki WIDE BANDGAP SEMICONDUCTORS: edited by Stephen J Pearton Ceramic and Other Materials—Processing and Technology ADVANCED CERAMIC PROCESSING AND TECHNOLOGY, Volume 1: edited by Jon G P Binner CEMENTED TUNGSTEN CARBIDES: by Gopal S Upadhyaya CERAMIC CUTTING TOOLS: edited by E Dow Whitney CERAMIC FILMS AND COATINGS: edited by John B Wachtman and Richard A Haber CORROSION OF GLASS, CERAMICS AND CERAMIC SUPERCONDUCTORS: edited by David E Clark and Bruce K Zoitos FIBER REINFORCED CERAMIC COMPOSITES: edited by K S Mazdiyasni FRICTION AND WEAR TRANSITIONS OF MATERIALS: by Peter J Blau HANDBOOK OF CERAMIC GRINDING AND POLISHING: edited by Ioan D Marinescu, Hans K Tonshoff, and Ichiro Inasaki HANDBOOK OF HYDROTHERMAL TECHNOLOGY: edited by K Byrappa and Masahiro Yoshimura HANDBOOK OF INDUSTRIAL REFRACTORIES TECHNOLOGY: by Stephen C Carniglia and Gordon L Barna SHOCK WAVES FOR INDUSTRIAL APPLICATIONS: edited by Lawrence E Murr SOL-GEL TECHNOLOGY FOR THIN FILMS, FIBERS, PREFORMS, ELECTRONICS AND SPECIALTY SHAPES: edited by Lisa C Klein SOL-GEL SILICA: by Larry L Hench SPECIAL MELTING AND PROCESSING TECHNOLOGIES: edited by G K Bhat SUPERCRITICAL FLUID CLEANING: edited by John McHardy and Samuel P Sawan Other Related Titles HANDBOOK OF PHYSICAL VAPOR DEPOSITION (PVD) PROCESSING: by Donald M Mattox JMR- 10-Nov-00 Preface The term hydrothermal is purely of geological origin It was first used by the British geologist, Sir Roderick Murchison (1792–1871), to describe the action of water at elevated temperature and pressure in bringing about changes in the earth’s crust, and leading to the formation of various rocks and minerals Geologists carried out the earliest work on the hydrothermal technique in the 19th century in order to understand the genesis of rocks and minerals by simulating the natural conditions existing under the earth crust However, materials scientists popularized the technique, particularly during 1940s Schafhautl who obtained quartz crystals upon freshly precipitated silicic acid in a papin’s digestor carried out the first hydrothermal synthesis in 1845 Subsequently, hydrothermal synthesis of a wide variety of minerals was carried out, especially in Europe The largest-known single crystal formed in nature (beryl crystal of >1000 kg) and some of the largest quantities of single crystals created in one experimental run (quartz crystals of >1000 kg) are both of hydrothermal origin The first successful commercial application of hydrothermal technology began with mineral extraction or ore beneficiation in the 19th century With the beginning of the synthesis of large single crystals of quartz by Nacken (1946) and zeolites by Barrer (1948), the commercial importance of the hydrothermal technique for the synthesis of inorganic compounds was realized ix x Preface The general acceptance of plate tectonics theory some ½ decades ago garnered much interest in geochemical processes at plate boundaries which led to the discovery of hydrothermal activity in the deep sea directly on the Galapagos Spreading Center in 1977 and a large number of other spectacular submarine hydrothermal systems of global significance to ocean chemistry and geochemistry In fact, this discovery has led to a new thinking in marine biology, geochemistry and in economic geology, and has spawned an entirely new term, viz., hydrothermal ecosystems, which means water-containing terrestrial, subterranean, and submarine high temperature environments, which are the sites of investigations for many palaeobiologists and biologists looking for primitive forms of life It is strongly believed that the roots of life on earth can be found in hydrothermal ecosystems These ecosystems may also serve as an analog for the possible origin of life on Mars, where a similar environment might have existed or still exists Earth is a blue planet of the universe where water is an essential component Circulation of water and other components such as entropy (energy) are driven by water vapor and heat (either external or internal) Water has a very important role in the formation of material or transformation of materials in nature, and hydrothermal circulation has always been assisted by bacterial activity From mid-1970s, exploration of the advantages of hydrothermal reactions, other than the hydrometallurgical and crystal growth aspects, began in Japan, particularly with reference to the ceramic powder processing A team of researchers from the Tokyo Institute of Technology, Japan, did pioneering work in ceramic processing such as powder preparation, reaction sintering, hot isostatic processing, and so on In the last decade, the hydrothermal technique has offered several new advantages like homogeneous precipitation using metal chelates under hydrothermal conditions, decomposition of hazardous and/or refractory chemical substances, monomerization of high polymers like polyethylene terephthalate, and a host of other environmental engineering and chemical engineering issues dealing with recycling of rubbers and plastics (instead of burning), and so on The solvation properties of supercritical solvents are being extensively used for detoxifying organic and pharmaceutical wastes and also to replace toxic solvents commonly used for chemical synthesis Similarly, it is used to remove caffeine and other food-related compounds selectively In fact, the food and nutrition experts in recent years are using JMR- 10-Nov-00 Preface xi a new term, hydrothermal cooking These unique properties take the hydrothermal technique altogether in a new direction for the 21st century and one can forecast a slow emergence of a new branch of science and technology for sustained human development We have collected a moreor-less complete list of publications in hydrothermal technology and provided the statistical data to show the growing popularity of the technique (Figures 1.10–1.12) The main disadvantage of the hydrothermal system, as believed earlier, is the black-box nature of the apparatus, because one cannot observe directly the crystallization processes However, in the recent years, remarkable progress has been made in this area through the entry of physical chemists, and the modeling of the hydrothermal reactions and the study of kinetics of the hydrothermal processes, which have contributed greatly to the understanding of the hydrothermal technique One can understand the hydrothermal chemistry of the solutions more or less precisely, which provides a solid base for designing hydrothermal synthesis and processing at much lower pressure and temperature conditions The hydrothermal technique exhibits a great degree of flexibility, which is being rightly exploited by a large scientific community with diversified interests Hydrothermal processing has become a most powerful tool, in the last decade, for transforming various inorganic compounds and treating raw materials for technological applications Today, the hydrothermal technique has found its place in several branches of science and technology, and this has led to the appearance of several related techniques, with strong roots to the hydrothermal technique, involving materials scientists, earth scientists, materials engineers, metallurgists, physicists, chemists, biologists, and others Thus, the importance of hydrothermal technology from geology to technology has been realized In view of such a rapid growth of the hydrothermal technique, it is becoming imperative to have a highly specialized book on this topic There are thousands of articles and reviews published on the various aspects of science of hydrothermal research but, so far, the most comprehensive works on this topic were limited to reviews and edited books, and there is not even a single monograph or book available The first author, Dr K Byrappa, edited a book entitled Hydrothermal Growth of Crystals in 1990 for Pergamon Press, Oxford, UK During early 1995, the authors conceived an idea of writing this handbook and began collecting old records from various sources The writing of this handbook started in 1997 In this handbook, we have dealt with all the JMR 10-Nov-00 xii Preface aspects of hydrothermal research covering historical development, natural hydrothermal systems, instrumentation, physical chemistry of hydrothermal growth of crystals, growth of some selected crystals like quartz, berlinite, KTP, calcite, and hydrothermal synthesis of a host of inorganic compounds like zeolites, complex coordinated compounds (silicates, germanates, phosphates, tungstates, molybdates, etc) and simple oxides, native elements, and the hydrothermal processing of materials with an emphasis on future trends of hydrothermal technology in the 21st century Many publications on hydrothermal research, especially in the Russian journals, were not easily accessible to us Our Russian colleagues in the field of hydrothermal research extended great cooperation in this regard Especially, the help rendered by Dr L N Demianets, Dr V I Popolitov and Dr O V Dimitrova is highly appreciated The authors are very grateful for the help and encouragement extended by the senior people in this field like Prof Shigeyuki So- miya (Professor Emeritus), Prof N Yamasaki (Tohoku University, Japan), late Dr Bob Laudise (AT & T Bell Labs.), Prof Rustom Roy (Penn State University), Prof C N R Rao (Director, JNCASR), Prof R Chidambaram (Chairman, Atomic Energy Commission, India), Dr B P Radhakrishna (former Director, Dept of Mines & Geology), late Prof J A Rabenau (Max-Planck Institute of Physics, Stuttgart), Prof Ichiro Sunagawa, Prof J A Pask, Prof Paul Hagenmuller, Prof H L Barnes, late Prof Saito Shinroku, and Prof Toshiyuki Sata Both Prof So- miya and Prof Yamasaki spent several hours with the authors and provided fruitful discussion Their suggestions and comments have been included in this book We would like to extend our special thanks to the most active hydrothermal researchers of the present day, like Prof S Hirano, Prof M Hosaka, Prof K Yanagisawa, Prof T Moriyoshi (Director, RIST, Takamatsu), Prof S Komarneni, Prof R E Riman, Dr Don Palmer, Dr Dave Wesolowski, Dr S Taki, Prof K Arai, Prof T B Brill, Prof T M Seeward, Prof Yuri Gogosti, Prof K Bowen, Prof David A Payne, Prof Fred F Lange, and Prof Fathi Habashi, who have helped us by providing their results and data for inclusion in this book Our colleagues at the Tokyo Institute of Technology, like Prof Masato Kakihana, Prof Nabuo Ishizawa, Prof Eiichi Yasuda, Prof Akira Sawaoka, Prof Masatomo Yashima, Prof Yasuo Tanabe, Prof Masanori Abe, Prof Kazunari Domen, and Prof Kiyoshi Okada, extended great cooperation in our task Other Japanese friends, like Dr Yasuro Ikuma, Prof Tsugio Sato, Prof Koji Kajiyoshi, Dr Atsuo Ito, Dr E H Ishida, Prof Zenbee Nakagawa, JMR- 10-Nov-00 856 Handbook of Hydrothermal Technology Na R-silicates transition 452 Nanoporous membranes 354 NASICON 521 conductivity 538 stoichiometry 538 structure 533, 538 Native elements crystals hydrothermal synthesis 691 Natural calcite crystals 281 Natural colored gemstones sources 480 Natural hydrothermal systems research Natural quartz principal source 200 Nepheline 484 crystals 485, 486 Niobates 676, 679 antimony 679 bismuth 679 hydrothermal growth 676 Noble metal thermocouples 97 Noble metals hydrothermal synthesis 692 two types of reaction 692 Non-centrosymmetric organic crystals 402 Non-specific solvation 173 Non-tetrahedral cations properties 420 Nonstoichiometric composition stability 296 Novel autoclaves 118 designs 101 Nucleation 354, 359, 695 rate 359, 360 Nucleation centers 582 Nucleation theory 360 classical and modern 355 Olivine type motif 504 OLPF See Optical low pass filter Omega zeolite 352 Opposed anvil system 117 Optical low pass filter 200 Optical second harmonic generation 402 Optimal energy utilization Organic materials 817 Organic substances 354 Orthophosphates crystallization 528 Oxidation processes 399 Oxide semiconductors application 717 Oxides 702 mixed 739 molybdenum 649 Oxyfluorides 619, 633 Oxyfluorinated compounds 631 Oxymolybdates 648 Paratellurite crystal morphology 716 method of crystallization 715 solubility 715 Parr autoclaves 129 Paulingite 325 Pegmatite crystallization 16 Pendulum Apparatus 120 Penta-antimonites 731, 732 Pentafluorides 621 Pentasils 401 Perovskite oxides 132 crystallization kinetics 184 Perovskite type titanates 806 Phanerostable 54 Phase 166 boundaries 511 diagrams 166 relationships 166 rule 166 tranformations 458 transitions 381 Index Phase equilibria 291 data 15 Phillipsite 350 Phosphate anions 522 Phosphate systems phase equilibria studies 519 Phosphates 416, 417, 421 crystal chemistry 418 hydrothermal synthesis 523 study 519 synthesis 520, 533 Phosphoric acid 377 Phosphoro-oxygen anions degree of condensation 531 Phosphorus 15 Phosphorus atoms 522 pentavalent state 418 trivalent state 418 Phosphorus pentoxide 13 Photo-semiconductors 74 Photorefracting crystal 471 Physical properties of HAp 287 Physico-chemical aspects PVT-behavior 83 solubility 83 Physico-chemical considerations 172 Piezo- and ferroelectrics 74 Piezoelectric high frequency devices 222 Piezoelectric ultrahigh frequency devices 222 Piston cylinder apparatus 117 Plate tectonics theory 19 Platinum lining 90 Polychalcogenides 681 Polycrystalline hydroxyapatite disk 298 Polymerizable complex method 821 Polymorphism double fluorides 619 Polyphosphates crystallization 528 857 Population balance formalism 360 Porous cyrstalline aluminophosphates 334 Potassium carbonate 678 Potassium lithium hexatitanate 660 Potassium niobate crystals solubility isochore 119 Potassium oxalate 678 Potassium titanyl arsenate 269 Potassium titanyl phosphate 256 Potassium-zirconium heptafluoride 626 Pressure balance arrangement 90 Pressure balancing technique 93 Pressure measurements 99 Pressure of hydrogen 701 Pressure-temperature range 101 Pseudoboehmite 380 PTX diagrams 166 PVT apparatus 121 Pyrochlore structure modified 628 Pyrophosphates crystallization 546 morphological habits 546 morphological variations 553 Pyroxenes recrystallization 56 Pyrrhotite 672 Quartz 198 α − β transition 201 double refraction 200 hydrothermal growth 207 single crystal growth 199 solubility 203 stability field 454 structural defects 219 synthesis large crystals 201 tuning forks 200 variety of applications 200 world’s largest producer 70 858 Handbook of Hydrothermal Technology α-Quartz 199 Quartz autoclaves main advantage 105 Quartz crystals existence of defects 219 growth 203, 207 kinetic studies 203 parameters 207 structural defects 208 Quartz glass autoclaves 102 tube liners 92 tubes 102 Quartz resonators 220 R2O3 high silica concentration 454 Raman spectrascopy 344 Rare earth antimonites 732 Rare earth cation radii 521 Rare earth elements 427, 619 distribution and mobility 426, 428 heavier 503 high basicity 458 ionic radii 452 natural compounds 498 silicates 436 Rare earth fluorides 619 unique technological applications 626 Rare earth germanates 499 luminescence properties 517 Rare earth motif 452 Rare earth orthophosphates 532 Rare earth orthovanadates 567 flux method 568 Rare earth phosphate system phase equilibria study 523 phase formation 524 Rare earth phosphates 521, 531, 555 anhydrous 531 formation 522 growth 528 hydrothermal synthesis 523 hydrothermal technique 532 hydrous 531 synthesis 520 Rare earth series characteristic phase 429 Rare earth silicates 416, 426 properties 459 solubility 427 structural elucidation 502 synthesis 451 Rare earth titanates flux method 660 Rare earth tungstates mixed 637 Rare earth vanadates 567 growth rate 568 Rare-metal transport 14 Reaction cell 121 Reaction kinetics 148, 186 Reaction mixture composition 339 Reaction pathway 180 Reaction pressure 140 Reaction time on the crystallization 380 Redox reactions 19 Regency emerald 477 Rocking autoclaves fixed-volume systems 127 flexible-cell system 127 Rod mills 147 Role of templates 352 Ruby growth 710 solubility 710 Index Salts 354 Sapphire growth 710 solubility 710 SAW 577 See also Surface acoustic wave SCW 813 SCWO See Supercritical water oxidation Second harmonic generation 256 Secondary structural units 323 Seed crystals 365 Seed orientation 264 Seeds growth of berlinite 235 Selenides 391, 674 melt method 674 physical properties 676 Selenium crystals 694 Self-assembly 821 Shadowgraph technique 162 Shape-selective catalysis 392 SHG See Second harmonic generation Short-circuit path model 779 Si-O-Si bonding 434 Si-tetrahedra bond lengths and angles 416 stability 421 Si:O phases higher pressures 435 higher temperatures 434 Si:O ratio 435 Silica 335 autoclaves 188 precipitated 335 zeolites 380 Silicate framework connectivity decrease 435 Silicate growth hydrothermal conditions 467 Silicate melts 13 Silicate structures 420 Silicate technology 415 Silicates 416, 421, 467, 533 characteristic feature 457 chemical stability 428 crystal chemistry 418 highly condensed 454 Silicates and germanates structural comparison 424 Silver liners 94 Single crystals growth 183 Sinterability 775 Sintering additives 792 SiO2 principal forms 199 solubility 432 Slow heating method major drawback 232 Sodalite 327, 348 recrystallization 119 single crystals 374 Sodium orthozincosilicate 489 Sodium zinc germanate synthesis 515 Sodium zincosilicates synthetic 490 Sodium zirconium silicates 461 hydrothermally grown crystals 466 Soft solution electrochemical process 821 Soft solution processing 8, 821 Sol-gel method 290 Sol-gel processing 821 Solid catalysts 400 Solid solutions crystallization 761 Solid state reaction method 289, 290 Solid state reactions 775 Solid state sintering 736 Solid-phase transformation 336 859 860 Handbook of Hydrothermal Technology Solubility 175, 187, 189, 213, 214, 215, 226, 264, 274, 275 apparatus 121 curves for KTP 265 dependence 176 measurement 124 negative coefficient 121 of berlinite 227 of calcite 279 of crystals 186 of α-quartz 215 of quartz 213 of sphalerite 671 of zincite 188 positive coefficient 121 theoretical aspects 186 thermodynamic interpretation 229 thermodynamic principles 174 Solubility of AlPO4 227 temperature coefficient 231 Solubility of GaPO4 252 Solubility of HAp 297 Solubility of KTP 264 extensive study 265 Solution-mediated transport 336 Solvated ions 172 Solvation 172 Solvent dielectric constant 180 Solvothermal 7, 821 synthesis 771 Sonochemical breakdown of liquid phases 147 Sorption properties 392 Sorption uptakes 394 Source materials 335 Spectroscopic properties rare earth fluorides 623 Sphalerite 671 spontaneous crystallization 119 a-Spodumene 495, 496 Spontaneous nucleation 640 Stability of calcium phosphates 292 Stable complex formation 542 Steam agitated autoclaves 143 Steel autoclaves 57, 105, 113 Stibiotantalite 677 Stilbite 327 Strecker synthesis 21 Structure-stabilizing agents 352 Submarine hydrothermal systems 19 Submarine hydrothermal vents 21 Substitution hetervalent 654 Isovalent 654 Substrates fabrication 785 Sulfide interaction 668 Sulphide aqueous solutions thermodynamic data 181 Sulphides synthesis of 665 Supercritical aqueous systems 17 Supercritical water 178, 180 oxidation 813, 814 properties 813 structure and dynamics 180 Superionic phosphates growth technology 552 hydrothermal crystallization 542 stages of interactions 542 Superionic pyrophosphates 553 Supersaturated solution 165, 359 Surface acoustic wave 576 Sweeping 220, 221 process 221 Synthesis apatite 287 berlinite 248 calcite 279 chemical composition 338 diselenide 676 ditelluride 676 hydrogel 338 paratellurite 716 Index scandium penta-antimonite 732 siderite 285 silicates 57, 519 strontium hydrogarnet 729 sulfides 665 TiO2 718, 719 zeolites 364 Synthesized minerals hydrothermal method 470 Synthetic emeralds 480 Synthetic Fe3+ variety of elpasoite 627 Synthetic zeolites 318, 328, 335 Tantalates 676 antimony 679 bismuth 679 hydrothermal growth 676 Tectoaluminosilicates 340 Tectosilicates 316 Teflon 282 Teflon liners 93, 719 Teflon ring 105 Tellurides melt methods 674 physical properties 676 Tellurium crystals 694 Temperature and time 349 Temperature-pressure map 820 Templating 352, 821 Tensile strength 85 Terbium-activated yttrium 621 Ternary system 74 Test-tube bomb 111 Test-tube racks 109 Tetragonal crystals 623 Tetragonal rare earth silicates field of stability 452 Tetragonal scheelite 649 Tetrahedral complexes configuration 420 Tetramethylammonium hydroxide 767 861 Thermal inversion 225 Thermocouple calibration 97 measure temperatures 97 Thermodynamics 64, 695 Thin film formation 133 Thin films growth 777 Thomsonite 365 Three-electrode technique 134 TiO2 application 725 photocatalytic activity 718 Titanates alkali 655 crystal chemistry 651 crystallization 651 rare earth 655 synthesis 650 technological applications 655 Titanium 650 alloy 85 dioxide 656 elucidation 653 oxides 712 silicates 461 Titanium bearing compounds isomorphism 655 Titanophosphate zeolites 317 Titanosilicate zeolites 399 Top seeded solution growth 562 Tourmaline 483 Tracer technique 779 Transition metal flourides 633 synthesis 626 Transition metal fluorocarbonates 3d 629 Transitional metal fluorocarbonates 3d 630 Transitional metal silicates 416 Transport and deposition mechanisms 11 Triangular cationic planes 631 Triisopropylbenzene 398 862 Handbook of Hydrothermal Technology Trioxides of tungsten 642 Trivalent metal titanates 660 Tungstates 636 Tungsten carbide-cobalt composites 813 Tuttle autoclaves 107, 455 Tuttle cold-cone sealed autoclaves 122 Tuttle cold-seal vessel 111 Tuttle-type closure 109 Twinned 589 Twinning 546, 643 Ultraphosphates crystallization 528 Univalent metals simple sulfides 666 Vanadates 419 hydrothermal technique 562 synthesis 561 Vanadium-oxygen compounds 402 Vanadophosphosphate zeolites 317 Various shape-selective catalysis 392 Vaterite 273 Veberite Na2MgAlF7 627 Verneuil method 562, 712 Verneuil technique 707 Versatility of hydrothermal chemistry 348 Vibrational spectroscopic cells 139 Viscosity of water 177 Volatility of water 290 Vuonnemite 655 Water as a guest molecule 348 PVT measurements 178 temperature - density diagram 180 Wave plate 200 Welded closure 112 Welded liner 113 Wet chemical method 289, 290 Wet chemical processing 821 Whisker 793 crystallite growth 794 Whiskers of HAp 40 Willemite 488 Wolframites of divalent metals 637 World wide web for zeolites Europe 319 North America 319 Wulfenite 646 X-ray techniques 199 X-ray topography horizontal gradient 242 Yield strength 85 Young’s modulus of bone 793 Yttrium aluminum garnet 734 Yttrium orthovanadate 562 Yttrium series 429 Zeolite synthesis 332, 336, 351 Zeolites applications 391 as catalysts 392 chemistry 323 crystal growth 364 crystallization 351, 361 detailed structural classification 323 formation 327, 331, 335, 349 genetic types 327 Index laboratory synthesis 328 lattice 352 minerals 315 nomenclature 325 phase-pure 185 silica composite films 384 structure 316, 319, 324 study of 404 synthesize 331 Zeolitization 331, 335, 352 Zinc oxide 703 Zincite crystals 706 growth 705 solubility 704 Zincogermanates hydrothermal growth 515 Zincosilicates hydrothermal synthesis 486 Zirconia 773 Zirconium germanate crystallization 511 Zirconium mineral 465 Zirconium oxides 712 Zirconium silicates 461, 466 Zone melting 562 863 Acknowledgments Figure 1.1 Courtesy of the American Geophysical Union, Washington, DC Figure 1.4 Courtesy of the American Geophysical Union, Washington, DC Figure 1.5 Courtesy of the American Geophysical Union, Washington, DC Figure 2.4 Courtesy of the American Chemical Society, Washington, DC Figure 2.7 Figure 3.5 Courtesy of the VEB Deutscher Verlag, Germany Courtesy of the Elsevier Science Publishers, Oxford, UK Courtesy of the American Chemical Society, Washington, DC Courtesy of the Elsevier Science Publishers, Oxford, UK Courtesy of the Clarendon Press, Oxford, UK Figure 3.13 Figure 3.16 Figure 3.17 Figure 3.20a Courtesy of the Elsevier Science Publishers, Oxford, UK 864 Acknowledgments 865 Figure 3.20b Courtesy of the American Institute of Physics, Washington, DC Figure 3.21 Courtesy of the Elsevier Science Publishers, Oxford, UK Figure 3.23 Courtesy of the Kluwer Academic /Plenum Publishers, New York Figure 3.24a Courtesy of the Kluwer Academic /Plenum Publishers, New York Figure 3.24b Courtesy of the American Chemical Society, Washington, DC Figure 3.26 Courtesy of the Kluwer Academic /Plenum Publishers, New York Figure 3.30 Courtesy of the American Chemical Society, Washington, DC Figure 3.31 Courtesy of the American Chemical Society, Washington, DC Figure 3.34 Figure 3.36 Figure 5.10 Courtesy of the Materials Research Society of Japan Courtesy of the Kluwer Academic /Plenum Publishers, New York Courtesy of the Elsevier Science Publishers, Oxford, UK Courtesy of the American Ceramic Society, Westerville, Ohio Courtesy of the Akademische Verlagsgesellschaft, Germany Courtesy of the Wiley Interscience Publications, New York Courtesy of the Elsevier Science Publishers, Oxford, UK Courtesy of the American Chemical Society, Washington, DC Courtesy of the NRC Research Press, Ottawa, Canada Figure 5.11 Courtesy of the NRC Research Press, Ottawa, Canada Figure 4.4 Figure 4.10 Figure 5.1 Figure 5.3 Figure 5.8 Figure 5.9 JMR 10-Nov-00 866 Acknowledgments Figure 5.13 Courtesy of the American Chemical Society, Washington, DC Figure 5.36 Courtesy of the Akademische Verlagsgesellschaft, Germany Figure 5.37 Courtesy of the Elsevier Science Publishers, Oxford, UK Figure 5.38 Courtesy of the Elsevier Science Publishers, Oxford, UK Figure 5.39 Courtesy of the Elsevier Science Publishers, Oxford, UK Figure 5.41 Courtesy of the Elsevier Science Publishers, Oxford, UK Figure 5.44 Courtesy of the Elsevier Science Publishers, Oxford, UK Figure 5.46 Courtesy of the Elsevier Science Publishers, Oxford, UK Figure 5.47 Figure 5.48 Courtesy of the Nippon Seramikkusu Kyokai, Tokyo Courtesy of the Elsevier Science Publishers, Oxford, UK Courtesy of the Elsevier Science Publishers, Oxford, UK Courtesy of the Elsevier Science Publishers, Oxford, UK Courtesy of the Elsevier Science Publishers, Oxford, UK Courtesy of the Wiley Interscience Publications, New York Courtesy of the Elsevier Science Publishers, Oxford, UK Courtesy of the Wiley Interscience Publications, New York Courtesy of the American Chemical Society, Washington, DC Figure 5.51 Figure 5.53 Figure 5.54 Figure 6.2 Table 6.3 Table 6.4 Figure 6.3b JMR- 10-Nov-00 Acknowledgments 867 Figure 6.6 Courtesy of the American Chemical Society, Washington, DC Table 6.10 Figure 6.11 Courtesy of the Academic Press, London, UK Courtesy of the Royal Society of Chemistry, Cambridge, UK Courtesy of the Royal Society of Chemistry, Cambridge, UK Courtesy of the Royal Society of Chemistry, Cambridge, UK Courtesy of the Royal Society of Chemistry, Cambridge, UK Courtesy of the Academic Press, London, UK Figure 6.12 Figure 6.13 Figure 6.14 Figure 6.15 Table 6.16 Figure 6.28 Figure 6.29 Figure 6.30 Figure 6.31 Figure 6.32 Figure 6.33 Figure 6.34 Figure 6.35 Figure 6.36 Figure 6.37 Courtesy of the Academic Press, London, UK Courtesy of the American Chemical Society, Washington, DC Courtesy of the Elsevier Science Publishers, Oxford, UK Courtesy of the Elsevier Science Publishers, Oxford, UK Courtesy of the Elsevier Science Publishers, Oxford, UK Courtesy of the Elsevier Science Publishers, Oxford, UK Courtesy of the American Chemical Society, Washington, DC Courtesy of the American Chemical Society, Washington, DC Courtesy of the American Chemical Society, Washington, DC Courtesy of the American Chemical Society, Washington, DC Courtesy of the American Chemical Society, Washington, DC JMR 10-Nov-00 868 Acknowledgments Figure 6.38 Courtesy of the Royal Society of Chemistry, Cambridge, UK Figure 6.42 Courtesy of the American Chemical Society, Washington, DC Figure 6.43 Courtesy of the American Chemical Society, Washington, DC Figure 6.44 Courtesy of the American Chemical Society, Washington, DC Figure 6.45 Courtesy of the American Chemical Society, Washington, DC Figure 6.46 Courtesy of the American Chemical Society, Washington, DC Figure 6.48 Courtesy of the Wiley Interscience Publications, New York Figure 6.49 Courtesy of the Wiley Interscience Publications, New York Figure 7.17 Figure 7.18 Courtesy of the IUCr Courtesy of the American Institute of Physics, Washington, DC Courtesy of the American Institute of Physics, Washington, DC Courtesy of the Elsevier Science Publishers, Oxford, UK Courtesy of the Elsevier Science Publishers, Oxford, UK Courtesy of the Elsevier Science Publishers, Oxford, UK Courtesy of the Elsevier Science Publishers, Oxford, UK Courtesy of the Elsevier Science Publishers, Oxford, UK Courtesy of the Elsevier Science Publishers, Oxford, UK Figure 7.27 Figure 7.28 Figure 7.30 Figure 7.32 Figure 7.38 Figure 8.1 Figure 8.2 JMR- 10-Nov-00 Acknowledgments 869 Figure 8.3 Courtesy of the Wiley Interscience Publications, New York Figure 8.4 Courtesy of the Wiley Interscience Publications, New York Figure 8.5 Figure 9.1 Courtesy of the Springer-Verlag, Germany Courtesy of the Springer-Verlag, Germany Figure 9.3 Figure 9.8 Courtesy of the Springer-Verlag, Germany Courtesy of the Prentice Hall Inc New Jersey, USA Figure 9.18 Courtesy of the Elsevier Science Publishers, Oxford, UK Figure 9.19 Courtesy of the American Chemical Society, Washington, DC Figure 9.21 Courtesy of the Kluwer Academic /Plenum Publishers, New York Figure 9.28 Courtesy of the Elsevier Science Publishers, Oxford, UK Figure 9.30 Courtesy of the Nippon Seramikkusu Kyokai, Tokyo Figure 9.31 Courtesy of the American Chemical Society, Washington, DC Figure 9.32 Courtesy of the Elsevier Science Publishers, Oxford, UK Table 10.4 Courtesy of the American Ceramic Westerville, Ohio Table 10.6 Courtesy of the Kluwer Academic /Plenum Publishers, New York Table 10.7 Table 10.8 Courtesy of the Materials Research Society, USA Courtesy of the Materials Research Society, USA Figure 10.8 Courtesy of the American Ceramic Westerville, Ohio Society, Figure 10.9 Courtesy of the American Ceramic Westerville, Ohio Society, Figure 10.20 Courtesy of the Kluwer Academic /Plenum Publishers, New York Society, JMR 10-Nov-00 870 Acknowledgments Figure 10.23 Courtesy of the Kluwer Academic /Plenum Publishers, New York Figure 10.33 Courtesy of the Elsevier Science Publishers, Oxford, UK Figure 10.34 Courtesy of the Kluwer Academic /Plenum Publishers, New York Figure 10.35 Courtesy of the Kluwer Academic /Plenum Publishers, New York JMR- 10-Nov-00 [...]... Vishwanathiah, late Prof B V Govindarajulu, Prof J A K Tareen, Prof D D Bhawalkar, Dr Krishan Lal, Dr R V Anantha Murthy, Prof A B Kulkarni, Prof T R N Kutty, Prof P N Satish, Dr B Basavalingu, Prof H L Bhat, Dr K M Lokanath Rai, and Dr M A Shankara), Russia (Prof V S Balitsky, Prof V A Kuznetsov, Prof D Yu Pushcharovsky, Dr Oleg Karpov, Dr G I Dorokhova, and Dr E Strelkhova), Korea (Prof Choy Jin-ho and Prof... the formation of various rocks and minerals.[1] A majority of the minerals formed in the postmagmatic and metasomatic stages in the presence of water at elevated pressure and temperature conditions are said to be “of hydrothermal origin.” This covers a vast number of mineral species including ore deposits It is well known that the largest single crystal formed in nature (beryl crystal of >1000 gm) and. .. aqueous media above 100°C and 1 bar.[15] Lobachev (1973) defined it as a group of methods in which crystallization is carried out from superheated aqueous solutions at high pressures.[16] Roy (1994) declares that hydrothermal synthesis involves water as a catalyst and occasionally as a component of solid phases in the synthesis at elevated temperature (>100°C) and pressure (greater than a few atmospheres).[17]... Mr B V Suresh Kumar, Mrs B Nirmala, Mr J R Paramesha, Mr Dinesh, Dr W Suchanek, and Dr S Srikanta Swamy is greatly appreciated Miss S Vidya, secretary of Prof K Byrappa, typed the manuscript Mr Murruli of Microsystems, Mysore, did the scanning of drawings, figures and photographs The manuscript was read and corrected for typographical errors and English usage by Dr K T Sunitha, Chair, Dept of English,... technique for the synthesis of inorganic compounds in a commercial way was realized soon after the synthesis of large single crystals of quartz by Nacken (1946) and zeolites by Barrer (1948) during late 1930s and 1940s, respectively.[6][7] The sudden demand for the large size quartz crystals during World War II forced many laboratories in Europe and North America to grow large size crystals Subsequently,... hydrothermal research.[11][12] In recent years, with the increasing awareness of both environmental safety and the need for optimal energy utilization, there is a case for the development of nonhazardous materials These materials should not only be compatible with human life but also with other living forms or species Also, processing methods such as fabrication, manipulation, treatment, reuse, and recycling... and Nayan (Prof Byrappa’s family members), Mrs Akiko Yoshimura, Sayaka, Ayumi, and Hirono (Prof Yoshimura’s family members) for their great patience and cooperation with us during these 3½ years of book writing We would like to acknowledge the financial support received from Japan Society for Promotion of Science (JSPS), New Energy and Industrial Technology Development Organization (NEDO), Japan, and. .. hydrothermal technique can be largely attributed to the rapid advances in the apparatus involved (new apparatus designed and fabricated) in hydrothermal research, and also to the entry of a large number of physical chemists, who have contributed greatly to the understanding of hydrothermal chemistry.[10] Further, the modeling and intelligent engineering of the hydrothermal processes have also greatly enhanced... Ikornikova, N Yu Hydrothermal Synthesis of Crystals in Chloride Systems Nauka, Moscow (1975) 5 Kuzmina, I P and Khaidukov, N M Crystal Growth from High Temperature Aqueous Solutions Nauka, Moscow (1977) 6 Demianets, L N., Labachev, A N., & Emelechenko, G A Germanates of Rare Earth Elements Nauka, Moscow (1980) 7 David T Rickard Frans E Wickman (ed.) Chemistry and Geochemistry of Solutions at High Temperature... especially under supercritical conditions These properties have been exploited appropriately in the recent years to disintegrate toxic organics, and recycle or treat waste materials In nature, also, water plays an important role in the formation of various rocks and minerals and in the creation of life (origin of life) As a component of granitic melts, H2O depresses solidus and liquidus temperatures,[40][41] ... Prof Masato Kakihana, Prof Nabuo Ishizawa, Prof Eiichi Yasuda, Prof Akira Sawaoka, Prof Masatomo Yashima, Prof Yasuo Tanabe, Prof Masanori Abe, Prof Kazunari Domen, and Prof Kiyoshi Okada, extended... ULTRA-FINE PARTICLES: edited by Chikara Hayashi, R Ueda and A Tasaki WIDE BANDGAP SEMICONDUCTORS: edited by Stephen J Pearton Ceramic and Other Materials Processing and Technology ADVANCED CERAMIC PROCESSING. .. on a large scale to prepare piezoelectric, magnetic, optic, ceramic and a host of other materials both as single crystals and polycrystalline materials In the recent years, several new advantages